CN107546422A - A kind of additive package of lead accumulator and preparation method thereof - Google Patents
A kind of additive package of lead accumulator and preparation method thereof Download PDFInfo
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- CN107546422A CN107546422A CN201710752462.2A CN201710752462A CN107546422A CN 107546422 A CN107546422 A CN 107546422A CN 201710752462 A CN201710752462 A CN 201710752462A CN 107546422 A CN107546422 A CN 107546422A
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention provides a kind of additive package of lead accumulator and preparation method thereof, described additive package is mixed by 100 parts by volume silicon compositions and 3~30 parts by volume aerosils；Described silicon composition, which is based on 100 parts by volume, to be included：Main chain backbone is the parts by volume of organosiloxane 1~10 of (C Si O) structure and side base containing more than one unsaturated hydrophilic active groups；The parts by volume of organic silicone oil 1~10；The parts by volume of industrial pure water 79.5~97.95；The parts by volume of emulsifying agent 0.05~0.5；Described additive package is prepared by process of the present invention, and its mix sulphur acid solution is added inside lead accumulator, can be strengthened the anti-softening of positive active material and be recovered hardening capacity, have few, the cost-effective advantage of addition.
Description
Technical field
The present invention relates to the field of material technology of lead accumulator, more particularly to a kind of additive package of lead accumulator
Material, formula and preparation method thereof.
Background technology
Lead accumulator abbreviation battery, in high-power/Large Copacities such as electrically propelled traction vehicle, car and boat starting, communication equipment station, energy storage
Field occupies empery status；In recent years with photovoltaic generation industry, the development of wind power industry, market common requirements great Rong
The battery of amount makees energy storage with applying mechanically, but conventional battery shows short life in use out of doors, and it is higher to discard rate, constrains
The business application of photovoltaic energy storage system.Industry is generally accepted, and appropriate colloidal substance is added in the sulfuric acid liquid of lead accumulator, can
Effectively lift the life-span used out of doors.
The colloidal materials that lead accumulator industry tradition uses are aerosil, during use by industrial pure water or other
Solvent method fully liquefies aerosil；In Chinese invention patent ZL01104182.X, disclose a kind of by poly- member
The silicon composition of organic siloxane, methyl-silicone oil and thinned water mixing is known as, said composition mixes to gather with sulfuric acid liquid is used as lead
The electrolyte or forming liquid of battery.Applied by ten several years, industry generally believes aerosil colloid and organic high score
Sub- colloid is each has something to recommend him, and the former viscosity is high, the income of manufacturability difference and lead accumulator without reduction internal resistance, increase capacity, but the life-span
Decay is more steady, and the latter's viscosity is low, good manufacturability and lead accumulator can obtain the income for reducing internal resistance, increasing capacity, but stably
Property is not so good as the former.
In recent years since, lead accumulator industry is seeking to one kind can be by aerosil colloid and silicon composition glue
The technical scheme that body has complementary advantages, but some methods and unsuccessful for simply mixing both, technical reason is：Conventional gas phase
Silicon dioxide colloid is a kind of aqueous-phase material, but described silicon composition is a kind of hydrophily oil phase thing, and both are simply mixed
The fine dispersion system closed and formed is unstable, and it is unsatisfactory to be added into the performance of the lead accumulator electrochemistry after electrolyte.Therefore,
Industry wishes to seek to one kind after aerosil fully can be coupled with silicon composition, be added into sulfuric acid liquid to be lifted
The colloid mixture additive of lead accumulator chemical property, lead accumulator is effectively extended outdoor service life, reduce and store
The discarded rate of battery.
The content of the invention
It is an object of the invention to：For aerosil colloid and organosilicon group in current lead accumulator industry market
The technological deficiency of compound colloid, there is provided a kind of that aerosil and silicon composition are fully coupled, are added into sulfuric acid liquid
The colloidal additive of lead accumulator chemical property can be lifted by making electrolyte, lead accumulator is effectively extended discharge and recharge and used the longevity
Life, reaching reduces technology application target of the battery using discarded rate.
To achieve the above object, the invention provides a kind of additive package of lead accumulator, described mixing addition
Agent is mixed by 100 parts by volume silicon compositions and 3~30 parts by volume aerosils；
Described silicon composition is based on 100 parts by volume, including following components and content：
Component A：Main chain backbone is (- C-Si-O-) structure and side base contains more than one unsaturated hydrophilic active group R, divided
Organosiloxane of the son amount less than 3000,1~10 parts by volume；
B component：Viscosity is less than the organic silicone oil of 2000 pas, 1~10 parts by volume；
Industrial pure water：79.5~97.95 parts by volume；
The parts by volume of emulsifying agent 0.05~0.5, described emulsifying agent include the one or more of following material：TWEEN Series breast
Agent, Span series emulsifying agent, triethanolamine, sodium carboxymethylcellulose, polyvinyl alcohol.
In the content of above-mentioned aerosil, described parts by volume is the scaled value of its weight/proportion；
In the component of above-mentioned additive package, the R contained by the component A organosiloxane side base includes H, OH, SO2H、
NH2、CH3Or other unsaturated hydrophilic active groups.
In the component of above-mentioned additive package, the organic silicone oil of the B component includes methyl-silicone oil, ethyl silicon oil, phenyl
Silicone oil, Methyl Hydrogen Polysiloxane Fluid, methyl phenyl silicone oil, cyanoethyl methyl polysiloxane or the organic silicone oil containing other organic groups.
In the component of above-mentioned additive package, the alkalescence adjustment that preparation process is used to adjust mixture pH value is additionally included in
Agent.Described alkaline regulator includes but is not limited to use sodium hydroxide or potassium hydroxide.
The material and ratio range of additive package based on above-mentioned lead accumulator, present invention also offers one kind by institute
The preparation method that stock is fabricated to the additive package of the lead accumulator is stated, this method includes：
1) described component A and described B component are thoroughly mixed uniformly；
2) HLB for the mixture for being obtained step 1) with described emulsifying agent is adjusted to 10~14；
3) mixture obtained to step 2) adds described industrial pure water, is thoroughly mixed uniformly, then adds institute
The alkaline regulator stated adjusts the pH value of mixture obtained by this step to 8-10；
4) mixture obtained to step 3) adds aerosil, is thoroughly mixed uniformly, that is, obtains the present invention
Described additive package.
In the preparation method of above-mentioned additive package, described step 4) also includes：As set-up procedure 3) obtained by mixing
The material ratio of thing and aerosil adjusts the clarity of this step mixture.
Present invention also offers a kind of lead storage battery electrolytic solution containing above-mentioned additive package or repair liquid.The electrolysis
The sulfuric acid liquid of liquid or reparation liquid using density as 1.05-1.35 is key component, body of the additive package in the electrolyte
Product content is not less than 0.2%, is not less than 2% in the volume content of the reparation liquid.
In the present invention, the viscosity for the additive package produced with the material prescription and preparation technology is low, is added into sulphur
Gel after acid solution is slow, is typically added into the sulfuric acid liquid a few hours and still meets technological requirement to lead accumulator routine liquid filling,
And versatility is good, can be used in mixed way with other conventional additives of lead storage battery electrolytic solution；Simultaneous Stabilization is good, adapts to storehouse
The commodity turnaround time needed for storage, transport and sales section.
Before have described, aerosil colloid and silicon composition colloid have respective advantage and disadvantage, industrial gas
The spatial volume of aerosil belongs to non-type structure, and when its average grain diameter is more than tens nanometer, produced is inorganic
Colloid viscosity is big, gel is overrun, filling process is poor, and it is low that the lead accumulator of supporting making shows as initial capacity；And foregoing have
If machine silicon composition can not be fabricated to the ball shape structure that particle diameter is less than 10 nanometers, the organic colloid that sulfuric acid liquid is produced is added into
Although viscosity is small, gel is slow, filling process is good, the chemical property of supporting making lead accumulator is equally undesirable, such as
Lead accumulator latter stage capacity attenuation speed is relatively large.
The additive package of the present invention can preferably overcome conventional gas-phase silicon dioxide colloid and silicon composition colloid
The shortcomings that, by above-mentioned material prescription and preparation method, it is abundant with silicon composition that inorganic aerosil can be obtained
The additive package of coupling, the additive package, which adds sulfuric acid liquid, to be had to the preferable percdation ability of positive electode of lead battery,
Positive electode of lead battery active material lattice avalanche speed caused by lead sulfate oxidationreduction can be slowed down, positive-plate life is given
(the major technique reason of lead accumulator end-of-life is caused by positive material(PAM) softening, accounts for end-of-life probability for extension
80%), now described additive package can be considered a kind of for extending the life-span reinforcing agent that uses of positive plate；When lead electric power storage
Pond because positive material(PAM) softening cause capacity attenuation when, by added inside lead accumulator it is a certain proportion of mixing add
Agent, it is pressurized make it internally plate group be evenly distributed after, positive-active can be made by secondary formation charging technique known to industry
Material hardens again, recover positive electrode capacity, and now described additive package can be considered a kind of for positive electrode capacity reparation
Repair solution additive.
A kind of additive package of lead accumulator of the present invention and preparation method thereof advantage is：
With the material prescription and preparation method of additive package of the present invention, can produce a kind of has work(to lead accumulator
The additive package of effect, the additive package are added into sulfuric acid liquid and make electrolyte by a certain percentage, can effectively lift lead accumulator
Chemical property, and can be used as a kind of positive electrode capacity repair additive of lead accumulator, while can be with other hydrophilic lead
Battery additive is used in mixed way, and purposes is wide, and using effect is good.
Embodiment
With reference to embodiment further to a kind of material of the additive package of lead accumulator of the present invention, match somebody with somebody
Side and its and its prepare process be described in detail.
Component A organosiloxane of the present invention is a species in organosilicon material, and its architectural feature is main chain
Skeleton has m (- C-Si-O-) segments, the positive integer of described m Wei≤1, and its side base (side chain) contains more than one insatiable hunger
With hydrophilic active group R, wherein described R includes but is not limited to H, OH, SO2H、NH2、CH3Deng or other are unsaturated
Hydrophilic active group；In numerous main chain backbones in the organosiloxane of (- C-Si-O-) segmented structure, all side bases (side chain) contain
The poly- element siloxanes for having unsaturated hydrophilic active group can select with B component organic silicone oil be coupled, for ensure component A and
B component is easier to be coupled under normal conditions, and is easily diluted after being copolymerized with B component, the A that molecular weight should be selected to be less than 3000
Component.
Another species in the organic silicone oil category organosilicon material of the B component, also known as silicone grease, silicon emulsion etc., it is described
Organic silicone oil include methyl-silicone oil, ethyl silicon oil, phenyl silicone oil, Methyl Hydrogen Polysiloxane Fluid, methyl phenyl silicone oil, cyanoethyl methyl polysiloxane or
Organic silicone oil containing other organic groups, there is the chain structure of different polymerization degree, with chain hop count n increases, molecular weight increases,
Viscosity increases, and viscosity should be selected during application to be less than the product of 2000 pas；B component additive package of the present invention important function it
One, it is the end-capping reagent of the molecular structure segment as component A, a kind of two-phase interface theory of electrochemistry thinks, (A+B) copolymerization shape
Into special compound bone add the set directed movement that sulfate liquid system is more beneficial for ion cluster, increase ion is in the channel
The ability of transition, be advantageous to be formed the absorption electric double layer of dynamic equilibrium in electrode and electrolyte two-phase interface, strengthen ion in electricity
The activation energy of pole surface reaction, accelerates electrode reaction speed, strengthens the high current respond of electrode.
Described industrial pure water is also known as industrial water, deionized water etc., because common source water salt content and pH value not
Together, these trace impurities can influence the production effect of the additive package；Industrial pure water is routinely that source water is passed through into electrodialysis
Device method, ion-exchanger method, hyperfiltration and be made, industrial pure water of the present invention, the ion removed includes cation
And anion, technical requirements resistivity is more than 10 megohms.
Described emulsifying agent is used to prepare the hydrophile-lipophile balance of (A+B) copolymer described in additive package procedure regulation
It is worth (HLB), the experiences that are about worth of HLB is estimated according to water-soluble method, the HLB of (A+B) copolymer being typically prepared is 7~9, directly
It is undesirable, it is necessary to the HLB of (A+B) copolymer is adjusted to 10~14 ideal conditions to connect the effect disperseed with industrial pure water；Breast
The range of choice of agent is larger, and actual interpolation amount is to adjust the HLB of (A+B) copolymer to for the purpose of required condition.Described breast
Agent is the common articles for use of pharmacy/chemical industry, such as tween (polyoxyethylene sorbitan fatty acid ester) is a kind of non-
Ionic surfactant, oil-in-water (O/W) type emulsifying agent and the solubilizer of oil phase substance are widely used as, with other emulsifying agents such as
Spans shares the stability that can increase emulsifying agent.The HLB of various emulsifying agents is each variant, even the emulsification of same component
Agent, also its HLB can be influenceed because of content, purity difference, recommend to compound regulation in described emulsifying agent, such as use tween system
Row emulsifying agent and sapn (sorbitan fatty acid ester) serial emulsifying agent carry out compounding regulation.
Described aerosil (white carbon) is that a kind of colloid known to lead accumulator manufacturing prepares material, its
Chemical formula is SiO2, the concentrated phosphoric acid of hydrofluoric acid and heat is soluble in, bases and can be melted and worked；Aerosil because of particle diameter very
Small, specific surface area is big, and superficial attractive forces are strong, and surface energy is big, and chemical purity is high, and dispersive property is good, has in thermal resistance, resistance etc.
There is specific performance, be always lead accumulator manufacturing colloidal electrolyte with its superior stability, reinforcing and thixotropy
Traditional material.Due to aerosil impalpable structure and in foam-like is accumulated, easily floated by moving air, true volume
Difficult accurate measuring, therefore aerosil parts by volume of the present invention, recommend to use volume instead and with proportion multiply in practical operation
Long-pending parts by weight metering.
The effect of the alkaline regulator, be adjust mixture preparation process intermediate pH value, it include it is all can
Mixture is realized into pH value adjustment and the alkaline regulator of sediment will not be produced, alkaline regulator is in mixing of the present invention
For symbolic animal of the birth year to micro, material selection face is wider in the content of additive, but considers preferred sodium hydroxide or potassium hydroxide from cost performance.
Such as sodium hydroxide, its chemical formula are NaOH, are commonly called as caustic soda, caustic soda, caustic soda, it is a kind of highly basic, is common chemicals, easily
It is dissolved in water and forms alkaline solution.
The raw material of above-described additive package can be purchased commercially, and the purity of the aerosil will
Ask and reach 99.99%, the purity requirement of the component A, B component and emulsifying agent is at least technical pure, and SILVER REAGENT more preferably, works as synthesis
During the contaminant overstandard of raw material, the synthetic effect of the additive package is influenced whether, the additive package of contaminant overstandard is added
Enter to the electrolyte for being added into lead accumulator, lead accumulator increase self discharge can be caused or even produce other side effects, meeting simultaneously
Influence the storage period of the additive package.
The additive package of lead accumulator of the present invention can not use one kettle way to mix, and be followed after need to stocking up certain
Prepared by process, the preparation method includes：
1) described component A and described B component are thoroughly mixed uniformly；
2) HLB for the mixture for being obtained step 1) with described emulsifying agent is adjusted to 10~14；
3) mixture obtained to step 2) adds described industrial pure water, is thoroughly mixed uniformly, then adds institute
The alkaline regulator stated adjusts the pH value of mixture obtained by this step to 8-10；
4) mixture obtained to step 3) adds aerosil, is thoroughly mixed uniformly, that is, obtains the present invention
Described additive package.
Above-mentioned steps 2) in, when the regulation that the emulsifying agent of one-component does not reach to the HLB of (A+B) copolymer requires,
The two or more compoundings of foregoing emulsifying agent can be used.In step 3), the pH value of gained mixture is adjusted to 8-10, be in order that
Gained mixture is preferably coupled with aerosil in the basic conditions.Step 4) is in practical operation, due to gas phase two
The more difficult accurate measuring of actual volume of silica, the parts by weight metering that its parts by volume uses volume and proportion product instead are more convenient；
In the optimization operation of step 4), in addition to as regulating step 3) obtained by the material ratio of mixture and aerosil adjust
The clarity of mixture is saved, because the discreteness of the granular micro-structure of aerosil is big, shows as point of every batch operation
It is variant to dissipate clarity, can be by regulating step 3 when obtained mixture clarity deficiency (big generally with apparent viscosity))
The material ratio of gained mixture and aerosil adjusts the clarity of mixture, makes the quality of obtained mixture
More preferably.
In order that the quality of prepared additive package is more preferable, can also continue to increase conventional filtration work afterwards in step 4)
Skill.Described additive package, if desired for long-term storage or as commodity selling, can continue to fit after step 4) is completed to prepare
Amount adds alkaline regulator and adjusts its pH value to more than 10.
Being stirred in the preparation method can be carried out at normal temperatures and pressures, and described is stirred including rotatably stirring
Mix, the shearing stirring that periodicity or corner cut are random, can also heat, help reaction using compressive reaction kettle, such as in mixture
Be stirred during keep mixture temperature be 75 DEG C ± 15 DEG C；When adding reaction pressure to mix using reactor, kettle
Pressure is no more than 25MPa.
The additive package of lead accumulator of the present invention is a kind of typical micro- dispersoid, is successful journey
Degree associates larger with preparation method, and its production effect can be tested by Tyndall (Tyndall) phenomenon to colloidal dispersion；
It is known in industry, wavelength be 400-700mm light by microdispersed colloidal dispersion when, if dispersed colloidal particle is straight
Footpath, which is less than lambda1-wavelength, to be scattered, and current general experiment conclusion is：When colloidal dispersion system particle diameter≤
During 94nm, luminous intensity is hit in scattering and the biquadratic of wavelength is inversely proportional.The Tyndall phenomenon of prepared additive package is obvious, says
The making of bright additive package reaches Technology design target；Conversely, can verify made additive package system not into
Work(.
More deep personnel, above-mentioned steps 1 are studied for this area) it can pass through completely to the preparation method described in step 4)
Regulation of the different component in mixed process carries out equivalent substitution；Such as when the mobility of mixture obtained by step 1) is good enough
When, industrial pure water can be added after aerosil what is obtained again with step 2) by step 2) and step 3) union operation
Mixture mixes, though the preparation method of this kind of equivalent substitution is also operable, easily produces isomers, it is possible to has influence on final
Electrochemistry effect of mixture.
In the specific implementation of the present invention, different selections and the married operation that feeds intake, as final mixture Stabilized
Under the premise of, it is possible that the contradiction of clarity and electrochemistry effect, the latter are often related to the aobvious state degree of Tyndall phenomenon.
When can'tting eat one's cake and have it, electrochemistry effect is recommended preferably to refine formula and technique.
The technical advantage of this additive package is obvious, can be fabricated to a kind of pervasive additive agent electrolyte of lead accumulator, surely
It is periodically long, it is easy to store and transports, directly makes an addition to sulfuric acid liquid when using by a certain percentage as lead accumulator electrolyte, also may be used
It is used in mixed way with other conventional additives, when mixed with other additives, it is necessary first to when paying attention to mixed with other additives
Whether appearance precipitates or viscosity increases to and is difficult to be filled into inside lead accumulator, meanwhile, it is lifting lead as a kind of design object
The additive of accumulator property, it is necessary to completely examine to the performance of lead-acid battery for using other additives with, determined with cost performance
Fixed and other additives mixtures' ratios.
The electrolyte of lead accumulator sulfuric acid liquid, filling lead accumulator are prepared with additive package of the present invention
With the obvious technical advantage of following items：
1st, the stable coupling of inorganic aerosil and silicon composition is realized, is reached aerosil glue
The technical advantage of body and silicon composition colloid is complementary, and the additive package made is added into the sulfuric acid of lead accumulator
Liquid possesses the double technique advantage of aerosil colloid and silicon composition colloid；
2nd, after the colloid mixture additive is added to conventional sulfuric acid liquid, the life time decay of lead accumulator performance is more steady,
And lead accumulator can obtain increase capacity, reduce the income of internal resistance；
3rd, preferable anti-softening and capacity repairs effect to positive electode of lead battery active material.
4th, versatility is good：It can be used in mixed way with other conventional additives of lead accumulator；
5th, stability is good, adapts to storage, transports and sell the commodity turnaround time needed for each link.
Following examples are only used for further illustrating technical scheme, and these technical schemes can be used alone,
It can add or combine and use other mature technologies.
Embodiment 1
A kind of target is designed to add in lead accumulator sulfuric acid liquid, the mixed of the anti-softening ability of positive active material can be increased
Additive is closed, the additive package is mixed by 100 parts by volume silicon compositions and 3 parts by volume aerosils, its
In, in terms of 100 parts by volume, component and content are silicon composition：
Component A：There is the organosiloxane of some (- C-Si-O-) segmented structures using a kind of main chain backbone, its side base contains
H, molecular weight 1200, addition are 10 parts by volume；
B component：Viscosity be 1000 pas methyl-silicone oil, 10 parts by volume；
Industrial pure water：79.5 parts by volume；
The parts by volume of emulsifying agent 0.5：From span 20 and Tween 80, wherein Tween 80 is for 0.4 parts by volume, and span 20 is for 0.1
Parts by volume, actual amount can adjust；
The alkaline regulator that preparation process is used to adjust mixture pH value selects sodium hydroxide, and sodium hydroxide is adjusted as actual
The dosage of pH value uses, and is prepared after completing stock using following process：
1) component A of 10 parts by volume and the B component of 10 parts by volume are thoroughly mixed uniformly；
2) use two kinds of described emulsifying agents to compound, the HLB of (A+B) copolymer that step 1) obtains is adjusted to 12, works as institute
Standby emulsifying agent, which can not be realized, adjusts HLB to 12 target, as long as the HLB of (A+B) copolymer is more than 10, can continue to walk
It is rapid 3), otherwise it is described adjustment emulsifying agent component or content；
3) uniformly, then the mixture that the industrial pure water addition step 2) of 79.5 parts by volume is obtained, is thoroughly mixed
Described sodium hydroxide is added to adjust the pH value of mixture obtained by this step to 8；
4) by mixture obtained by step 3) on the basis of 100 parts by volume, the aerosil of 3 parts by volume is added, fully
15 minutes mixed above uniform, as described additive packages of gained mixture of stirring.
Above-mentioned preparation method is stirred at normal temperatures and pressures, and the additive package of gained need to such as be deposited for a long time, then in right amount
The described sodium hydroxide of addition stock, the pH value of the additive package is adjusted to 12.
The additive package that the present embodiment obtains can be as a kind of wide spectrum additive of lead accumulator sulfuric acid liquid, according to not
Same purposes adds different proportion in the sulfuric acid liquid of lead accumulator.
Embodiment 2
Additive package that embodiment 1 is obtained and lead accumulator sulfuric acid liquid that density is 1.245 by volume 1：99 is mixed
Closing, which uniformly, turns into a kind of organosilicon polymer, silica and sulfuric acid liquid, mixes poly- colloidal electrolyte.
The present embodiment electrolyte is filled into inside lead accumulator of the 2V500Ah energy storage with valve-regulated AGM diaphragm structures, passed through
After conventional dipping, formation charging, turning into one has the extraordinary colloid plumbic storage battery of resistant to elevated temperatures outdoor energy storage.The present embodiment
Additive package is with volume ratio 1：The filling lead accumulator of 99 mix sulphur acid solutions uses, and under the liquid-tight degree same case of sulfuric acid, can make
The effect that lead accumulator substantially obtains and reduces internal resistance, increases capacity.
In the present embodiment, the conventional anhydrous sodium sulfate of lead accumulator industry can be also added in described colloidal electrolyte,
Anhydrous sodium sulfate accounts for the 0.3% of the extraordinary colloidal electrolyte volume total amount, and industry is generally accepted, and one is added in colloidal electrolyte
Determine the anhydrous sodium sulfate of content, electrolyte electrochemical activity can be lifted, reduce the internal resistance of colloid plumbic storage battery, lift leaching colloidal
The charge acceptance of battery.
Embodiment 3
In embodiment 1, silicon composition and the volume proportion of aerosil that the step 3) is prepared are
100：3, additive package total amount is 103 parts by volume；The volume proportion is changed into 100 by the present embodiment：15, i.e. additive package
Total amount changes into 115 parts by volume, and preparation method is same as Example 1.
Typically contrast effect test result on probation is：Silicon composition is different from the proportioning of aerosil, mixes
Different electrochemical properties can be shown by closing additive, and when additive package is using silicon composition to be main, lead accumulator can
The income for obtain and reduce internal resistance, increasing capacity；And when increasing the mixed proportion of aerosil, what lead accumulator was shown
Cycle charge-discharge life time decay is more steady.
The additive package of the present embodiment is with volume ratio 1：The filling lead accumulator of 99 mix sulphur acid solutions uses, and can make lead electric power storage
The cycle charge discharge electric life in pond is better than the effect of embodiment 2.
Embodiment 4
Design another electrolyte additive package for adapting to the lead accumulator that long-term floating charge system uses, the additive package
Mixed by 100 parts by volume silicon compositions and 30 parts by volume aerosils, wherein, silicon composition is with 100
Parts by volume meter, component and content are：
Component A：Used organosiloxane is that main chain backbone has some (- C-Si-O-) segmented structures, and molecular weight is
1500, its side base contains SO2H, the parts by volume of addition 1；
B component：Viscosity be 1100 pas ethyl silicon oil, the parts by volume of addition 1；
Industrial pure water：97.95 parts by volume；
The parts by volume of emulsifying agent 0.05：It is standby for 0.04 parts by volume, span 40 from span 40 and Tween 80, wherein Tween 80
0.01 parts by volume, actual amount can adjust.
In the present embodiment, the alkaline regulator for adjusting mixture intermediate pH value uses potassium hydroxide, potassium hydroxide
Use by the dosage of actual adjustment pH value, prepared after completing stock using following process：
1) component A of 1 parts by volume and the B component of 1 parts by volume are thoroughly mixed uniformly；
2) use two kinds of described emulsifying agents to compound, the HLB of (A+B) copolymer that step 1) obtains is adjusted to 14, works as institute
Standby emulsifying agent, which can not be realized, adjusts HLB to 14 target, as long as the HLB of (A+B) copolymer is more than 10, can continue to walk
It is rapid 3), otherwise it is described adjustment emulsifying agent component or content；
3) uniformly, then the mixture that the industrial pure water addition step 2) of 97.95 parts by volume is obtained, is thoroughly mixed
Described potassium hydroxide is added to adjust the pH value of mixture obtained by this step to 10；
4) by the mixture that step 3) obtains on the basis of 100 parts by volume, the aerosil of 30 parts by volume is added,
Reaction is helped with pressurizeing and heating using reactor in aerosil mixed process, kettle pressure is 20MPa, is mixed using reactor
It is 75 DEG C ± 10 DEG C that the mixture temperature in kettle is kept during conjunction, is persistently stirred 30 minutes, and gained mixture is this
Additive package described in embodiment；Additive package obtained by this step is filtered, it is product to take filtrate.In this step, such as
Fruit mixture clarity deficiency or viscosity it is bigger than normal, as micro set-up procedure 3) obtained by the material of mixture and aerosil
Ratio adjusts the clarity of this step mixture.
Content of the present embodiment because of aerosil in mixing additive prescription is higher, is made with suitable after sulfuric acid liquid
Large Copacity lead accumulator, it is especially suitable for the outdoor Large Copacity energy storage lead accumulator for making long-term floating charge state.
Embodiment 5
The additive package that embodiment 1 is obtained uses the homogenizing processing of high-speed emulsifying machine, described high-speed emulsifying machine
Homogenizing rotary speed be more than 20000 revs/min, after the additive package homogenized deep processing processing, with the lead that density is 1.20
Electrolyte acid liquid by volume 1：10 mixing are uniformly dispersed, and turn into a kind of and repair the special of positive electode of lead battery active material
With additive, market is commonly called as repairing liquid or renovation agent.
The reparation liquid of the present embodiment is added into through being judged as positive material(PAM) softening and held by quantifying for 1ml/10Ah
Inside the lead accumulator for measuring decay, the inner panel group point through adding negative pressure technique to make the reparation liquid in lead accumulator known to industry
After cloth is uniform, by secondary formation charging technique known to industry, the positive plate active material of softening is hardened again, treat this
The positive plate active material of the lead accumulator of reparation recovers capacity again.
It should be noted last that the above embodiments are merely illustrative of the technical solutions of the present invention and it is unrestricted.Although ginseng
The present invention is described in detail according to embodiment, it will be understood by those within the art that, to the technical side of the present invention
Case is modified or equivalent substitution, and without departure from the spirit and scope of technical solution of the present invention, it all should cover in the present invention
Right among.
Claims (7)
1. a kind of additive package of lead accumulator, it is characterised in that described additive package is by 100 parts by volume organosilicons
Composition and 3~30 parts by volume aerosils mix；
Described silicon composition is based on 100 parts by volume, including following components and content：
Component A：Main chain backbone is (- C-Si-O-) structure and side base contains more than one unsaturated hydrophilic active group R, molecular weight
Organosiloxane less than 3000,1~10 parts by volume；
B component：Viscosity is less than the organic silicone oil of 2000 pas, 1~10 parts by volume；
Industrial pure water：79.5~97.95 parts by volume；
The parts by volume of emulsifying agent 0.05~0.5, described emulsifying agent include the one or more of following material：TWEEN Series emulsify
Agent, Span series emulsifying agent, triethanolamine, sodium carboxymethylcellulose, polyvinyl alcohol.
2. the additive package of lead accumulator according to claim 1, it is characterised in that the component A organosiloxane
R contained by side base includes H, OH, SO2H、NH2、CH3Or other unsaturated hydrophilic active groups.
3. the additive package of lead accumulator according to claim 1, it is characterised in that the organic silicone oil of the B component
Including methyl-silicone oil, ethyl silicon oil, phenyl silicone oil, Methyl Hydrogen Polysiloxane Fluid, methyl phenyl silicone oil, cyanoethyl methyl polysiloxane or organic containing other
The organic silicone oil of group.
4. the additive package of lead accumulator according to claim 1, it is characterised in that described additive package also wraps
Include in alkaline regulator of the preparation process for adjusting mixture pH value.
5. a kind of preparation method of the additive package based on any lead accumulator of Claims 1 to 4, including：
1) described component A and described B component are thoroughly mixed uniformly；
2) HLB for the mixture for being obtained step 1) with described emulsifying agent is adjusted to 10~14；
3) mixture obtained to step 2) adds described industrial pure water, is thoroughly mixed uniformly, then described in addition
Alkaline regulator adjusts the pH value of mixture obtained by this step to 8-10；
4) mixture obtained to step 3) adds aerosil, is thoroughly mixed uniformly, that is, obtains of the present invention
Additive package.
6. according to the method for claim 5, it is characterised in that described step 4) also includes：By set-up procedure 3) institute
The material ratio of mixture and aerosil adjusts the clarity of this step mixture.
7. the lead storage battery electrolytic solution containing any additive package of Claims 1 to 4 repairs liquid.
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| CN201710752462.2A CN107546422A (en) | 2017-08-28 | 2017-08-28 | A kind of additive package of lead accumulator and preparation method thereof |
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| CN201710752462.2A CN107546422A (en) | 2017-08-28 | 2017-08-28 | A kind of additive package of lead accumulator and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109830767A (en) * | 2019-03-04 | 2019-05-31 | 厦门恒正源新材料科技有限公司 | A kind of environmental protection lead-acid accumulator nanometer renovation agent and preparation method thereof |
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| CN1312331A (en) * | 2001-02-23 | 2001-09-12 | 刘粤荣 | Organic high molecular composite for accumulator and its preparation method |
| CN104218261A (en) * | 2014-08-15 | 2014-12-17 | 浙江天能电池江苏新能源有限公司 | Colloid electrolyte capable of improving service life of lead-acid cell |
| EP3021415A1 (en) * | 2014-11-13 | 2016-05-18 | F.I.A.M.M. S.P.A. | Additive for electrolyte of lead-acid batteries |
| WO2017098666A1 (en) * | 2015-12-11 | 2017-06-15 | 日立化成株式会社 | Lead storage battery |
| CN106876797A (en) * | 2015-12-13 | 2017-06-20 | 青岛祥智电子技术有限公司 | A kind of lead-acid accumulator electrolyte and preparation method thereof |
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2017
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1312331A (en) * | 2001-02-23 | 2001-09-12 | 刘粤荣 | Organic high molecular composite for accumulator and its preparation method |
| CN104218261A (en) * | 2014-08-15 | 2014-12-17 | 浙江天能电池江苏新能源有限公司 | Colloid electrolyte capable of improving service life of lead-acid cell |
| EP3021415A1 (en) * | 2014-11-13 | 2016-05-18 | F.I.A.M.M. S.P.A. | Additive for electrolyte of lead-acid batteries |
| WO2017098666A1 (en) * | 2015-12-11 | 2017-06-15 | 日立化成株式会社 | Lead storage battery |
| CN106876797A (en) * | 2015-12-13 | 2017-06-20 | 青岛祥智电子技术有限公司 | A kind of lead-acid accumulator electrolyte and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109830767A (en) * | 2019-03-04 | 2019-05-31 | 厦门恒正源新材料科技有限公司 | A kind of environmental protection lead-acid accumulator nanometer renovation agent and preparation method thereof |
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Application publication date: 20180105 |